Synthesis of Four Stereoisomers of 1,4-Thiazane-3-carboxylic Acid 1-Oxide via the Asymmetric Transformation (combined isomerization-preferential crystallization) of 1,4-Thiazane-3-carboxylic Acid
In order to synthesize four stereoisomers of 1,4-thiazane-3-carboxylic acid 1-oxide (TCA*SO), (S)-1,4-thiazane-3-carboxylic acid [(S)-TCA], which is one of the precursors, was prepared by the asymmetric transformation (combined isomerization-preferential crystallization) of (RS)-TCA. This asymmetric...
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Published in | Bioscience, biotechnology, and biochemistry Vol. 64; no. 2; pp. 341 - 347 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
England
Japan Society for Bioscience, Biotechnology, and Agrochemistry
01.02.2000
Oxford University Press |
Subjects | |
Online Access | Get full text |
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Summary: | In order to synthesize four stereoisomers of 1,4-thiazane-3-carboxylic acid 1-oxide (TCA*SO), (S)-1,4-thiazane-3-carboxylic acid [(S)-TCA], which is one of the precursors, was prepared by the asymmetric transformation (combined isomerization-preferential crystallization) of (RS)-TCA. This asymmetric transformation was used (2R, 3R)-tartaric acid [(R)-TA] as a resolving agent and salicylaldehyde as the epimerization catalyst in propanoic acid at 110°C to afford a salt of (S)-TCA with (R)-TA in 100% de with a yield of over 90%. Optically pure (S)-TCA was obtained by treating the salt with triethylamine in methanol in a yield of over 80%, based on (RS)-TCA as the starting material. In addition, asymmetric transformation of (R)-TCA gave (S)-TCA in a yield of 60-70%. (S)-TCA was oxidized by hydrogen peroxide in dilute hydrochloric acid to selectively crystallize (1S, 3S)-TCA*SO. (1R, 3S)-TCA*SO of 70% de from the filtrate was allowed to form a salt with (R)-TA after a treatment with triethylamine to give (1R, 3S)-TCA*SO as a single diastereoisomer. (1R, 3R)- and (1S, 3R)-TCA*SO were also prepared by starting from (R)-TCA that had been synthesized from L-cysteine. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0916-8451 1347-6947 |
DOI: | 10.1271/bbb.64.341 |